CN115651188B - RAFT chain transfer agent and preparation method and application thereof - Google Patents
RAFT chain transfer agent and preparation method and application thereof Download PDFInfo
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- CN115651188B CN115651188B CN202211324576.4A CN202211324576A CN115651188B CN 115651188 B CN115651188 B CN 115651188B CN 202211324576 A CN202211324576 A CN 202211324576A CN 115651188 B CN115651188 B CN 115651188B
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- polyethylene glycol
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- 239000012986 chain transfer agent Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 70
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 34
- 125000003827 glycol group Chemical group 0.000 claims abstract description 26
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000001841 imino group Chemical group [H]N=* 0.000 claims abstract description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 30
- -1 glycol thioester Chemical class 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 12
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 12
- 239000012312 sodium hydride Substances 0.000 claims description 12
- 229910052987 metal hydride Inorganic materials 0.000 claims description 11
- 150000004681 metal hydrides Chemical class 0.000 claims description 11
- 150000007970 thio esters Chemical class 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 150000003254 radicals Chemical group 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- CRRUGYDDEMGVDY-UHFFFAOYSA-N 1-bromoethylbenzene Chemical compound CC(Br)C1=CC=CC=C1 CRRUGYDDEMGVDY-UHFFFAOYSA-N 0.000 claims description 5
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 5
- XUHFBOUSHUEAQZ-UHFFFAOYSA-N bromobenzyl cyanide Chemical compound N#CC(Br)C1=CC=CC=C1 XUHFBOUSHUEAQZ-UHFFFAOYSA-N 0.000 claims description 5
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 5
- BJJVDFADUDDTQK-UHFFFAOYSA-N 5-hydroxy-2-methylpentanenitrile Chemical compound N#CC(C)CCCO BJJVDFADUDDTQK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 18
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 abstract description 15
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 9
- 239000012989 trithiocarbonate Substances 0.000 description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229920003169 water-soluble polymer Polymers 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000012991 xanthate Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 125000003088 (fluoren-9-ylmethoxy)carbonyl group Chemical group 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- HMHYBQHINBJJGL-UHFFFAOYSA-N 4-[(4-carboxy-4-cyanobutan-2-yl)diazenyl]-2-cyanopentanoic acid Chemical compound N#CC(C(O)=O)CC(C)N=NC(C)CC(C#N)C(O)=O HMHYBQHINBJJGL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- 229920003172 poly (isopropyl acrylamide) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a RAFT chain transfer agent, a preparation method and application thereof, wherein the RAFT chain transfer agent is positioned at the Z end by polyethylene glycol groups; the RAFT chain transfer agent has the structural formula:n is an integer of 1-1000, X is one of oxygen atom, sulfur atom and imino group, R 1 、R 2 Each independently selected from hydrogen atoms, substituted C 1 ‑C 18 Alkyl, unsubstituted C 1 ‑C 18 One of the alkyl groups, R 3 Selected from substituted C 1 ‑C 18 Alkyl, unsubstituted C 1 ‑C 18 Alkyl, substituted C 1 ‑C 18 Alkoxycarbonyl, unsubstituted C 1 ‑C 18 One of alkoxycarbonyl, substituted aryl, unsubstituted aryl, and cyano. In the RAFT chain transfer agent provided by the invention, the polyethylene glycol group is positioned at the Z end, so that the RAFT chain transfer agent has good water solubility in a wide pH environment, and the polymer end obtained through RAFT polymerization reaction does not contain polyethylene glycol group modification.
Description
Technical Field
The invention relates to the technical field of controllable free radical polymerization, in particular to a RAFT chain transfer agent and a preparation method and application thereof.
Background
Reversible addition-fragmentation chain transfer (Reversible addition-fragmentation chain transfer, RAFT) polymerization has wide application prospects in the controllable preparation and synthesis of high polymer materials, and is critical to RAFT chain transfer agents, however, most RAFT chain transfer agents are oil-soluble molecules, and are difficult to apply in the polymerization of water-soluble monomers such as acrylamide and the like.
The water-soluble RAFT chain transfer agents reported at present often contain charged groups such as amino groups, carboxyl groups and the like, but the solubility of the RAFT chain transfer agents is often greatly changed under the acid-base condition, so that the application of the RAFT chain transfer agents is restricted. The other water-soluble RAFT chain transfer agent is prepared by condensation reaction with a small molecular chain transfer agent with a specific functional group based on water-soluble polymers such as polyethylene glycol and the like, but on one hand, the connecting bond between the water-soluble polymers and the thioester chain transfer agent of the RAFT chain transfer agent is easy to hydrolyze, so that the stability problem exists; on the other hand, as the water-soluble polymer is modified on one side (namely the R end) of the growth center of the RAFT chain transfer agent, the final polymer product obtained by polymerization by using the RAFT chain transfer agent inevitably carries the water-soluble polymer, and the intrinsic property of the product is unnecessarily influenced; in addition, because of the need of introducing water-soluble polymer modification into the RAFT chain transfer agent, the R end of the small molecular chain transfer agent must have a corresponding condensable functional group, and the R group selection and the preparation method of the chain transfer agent are greatly limited. Therefore, developing RAFT chain transfer agents that have good solubility in a wide range of pH water environments without additional impact on the end product properties would facilitate wide use of RAFT polymerization in aqueous environments.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a RAFT chain transfer agent, a preparation method and an application thereof, and aims to solve the problems that the existing RAFT chain transfer agent is poor in solubility and other groups are inevitably introduced into a polymerization end product.
The technical scheme of the invention is as follows:
in a first aspect of the invention, there is provided a RAFT chain transfer agent wherein a polyethylene glycol group is located at the Z-terminus of the RAFT chain transfer agent; the RAFT chain transfer agent has a structural general formula:
wherein n is an integer of 1 to 1000, X is one of oxygen atom, sulfur atom and imino group, R 1 、R 2 Each independently selected from hydrogen atoms, substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 One of the alkyl groups, R 3 Selected from substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 Alkyl, substituted C 1 -C 18 Alkoxycarbonyl, unsubstituted C 1 -C 18 One of alkoxycarbonyl, substituted aryl, unsubstituted aryl, and cyano.
In a second aspect of the present invention, there is provided a method for preparing a RAFT chain transfer agent according to the present invention, comprising the steps of:
will beMixing metal hydride and carbon disulfide, and reacting to obtain polyethylene glycol thioester metal salt;
the polyethylene glycol thioester metal saltCarrying out substitution reaction to obtain the RAFT chain transfer agent;
wherein A is a halogen atom.
Optionally, the metal hydride is selected from at least one of sodium hydride and potassium hydride.
Optionally, the halogen atom is a chlorine atom, a bromine atom or an iodine atom.
Optionally, the saidSelected from one of benzyl bromide, (1-bromoethyl) benzene, bromobenzyl cyanide and ethyl 2-bromo-2-methylpropionate.
According to a third aspect of the present invention, there is provided a method for preparing a RAFT chain transfer agent according to the present invention, comprising the steps of:
will beMixing metal hydride, carbon disulfide and iodine, and reacting to obtain polyethylene glycol thioester disulfide;
the polyethylene glycol thioester disulfide is producedAnd (3) carrying out free radical exchange reaction on the compound to obtain the RAFT chain transfer agent.
Optionally, carrying out a free radical exchange reaction on the polyethylene glycol thioester disulfide and azobisisobutyronitrile or azobis (4-cyanoamyl alcohol) to obtain the RAFT chain transfer agent.
In a fourth aspect of the invention there is provided the use of a RAFT chain transfer agent according to the invention in a RAFT polymerisation reaction.
Alternatively, the RAFT polymerisation is carried out in the aqueous phase.
The beneficial effects are that: one end of the RAFT chain transfer agent provided by the invention is connected with a polyethylene glycol group (water-soluble group), so that the RAFT chain transfer agent has good water solubility in a wide pH environment, and is particularly suitable for a RAFT polymerization system in an acidic-alkaline aqueous environment; in addition, because the polyethylene glycol group is positioned at the Z end of the RAFT chain transfer agent, the end of the polymer obtained by the RAFT polymerization reaction does not contain polyethylene glycol group modification, so that a polymer product completely free of polyethylene glycol chain segments can be obtained after the conventional desulfurization ester reaction, and the intrinsic composition of the polymer macromolecule obtained by the RAFT polymerization reaction is not influenced.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the product obtained in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of the product obtained in example 5 of the present invention.
FIG. 3 is a nuclear magnetic resonance spectrum of the product obtained in example 8 of the present invention.
Detailed Description
The invention provides a RAFT chain transfer agent, a preparation method and application thereof, and aims to make the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The embodiment of the invention provides a RAFT chain transfer agent, wherein a polyethylene glycol group is positioned at the Z end of the RAFT chain transfer agent; the RAFT chain transfer agent has a structural general formula:
wherein n is an integer of 1 to 1000, X is one of oxygen atom, sulfur atom and imino group, R 1 、R 2 Each independently selected from hydrogen atoms, substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 One of the alkyl groups, R 3 Selected from substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 Alkyl, substituted C 1 -C 18 Alkoxycarbonyl, unsubstituted C 1 -C 18 One of alkoxycarbonyl, substituted aryl, unsubstituted aryl, and cyano.
In this embodiment, n is the polymerization degree of polyethylene glycol, and is an integer between 1 and 1000, i.e., n may be any integer between 1 and 1000, including 1 and 1000. For example, n may be 1, 10, 50, 100, 200, 300, 500, 600, 800, 900 or 1000, etc.
In this example, R can be selected or determined depending on the desired group of the final polymer product 1 、R 2 、R 3 . By way of example, R 1 、R 2 Each independently selected from hydrogen atoms, substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 One of alkyl groups, but not limited thereto; r is R 3 Selected from substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 Alkyl, substituted C 1 -C 18 Alkoxycarbonyl, unsubstituted C 1 -C 18 One of alkoxycarbonyl, substituted aryl, unsubstituted aryl, cyano, but is not limited thereto. It will be appreciated that C 1 -C 18 Alkyl refers to an alkyl group having 1 to 18 carbon atoms, e.g., C 16 Alkyl refers to an alkyl group having 16 carbon atoms; c (C) 1 -C 18 Alkoxycarbonyl groups are the same. Specifically, by way of example, C 4 Alkyl groups may be n-butyl, isobutyl or tert-butyl; substituted C 1 -C 18 The substituent in the alkyl group may be halogen, hydroxy, amino, carboxyl, etc.; aryl may be phenyl, pyridyl, or the like; the substituents in the substituted aryl groups can be alkyl, halogen, nitro, and the like; c (C) 1 -C 18 The alkoxycarbonyl group may be methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, t-butoxycarbonyl, or fluorenylmethoxycarbonyl, etc.; substituted C 1 -C 18 The substituent in the alkoxycarbonyl group may be halogen, hydroxy, amino, carboxy, etc.
In the embodiment of the invention, the RAFT chain transfer agent is a neutral water-soluble RAFT chain transfer agent, and one end of the RAFT chain transfer agent is connected with a polyethylene glycol group (water-soluble group), so that the RAFT chain transfer agent has good water solubility in a wide pH environment, and is particularly suitable for a RAFT polymerization system in an acid-base aqueous phase environment; in addition, because the polyethylene glycol group is positioned at the Z end of the RAFT chain transfer agent, the end of the polymer obtained by the RAFT polymerization reaction does not contain polyethylene glycol group modification, so that a polymer product completely free of polyethylene glycol chain segments can be obtained after the conventional desulfurization ester reaction, and the intrinsic composition of the polymer macromolecule obtained by the RAFT polymerization reaction is not influenced.
The specific principle is as follows:
the polyethylene glycol group of the existing RAFT chain transfer agent containing the polyethylene glycol group is modified on one side of a growth center (namely R end), and the reaction general formula of the RAFT chain transfer agent for carrying out polymerization reaction is shown as follows:
wherein n is the polymerization degree of polyethylene glycol, R can represent any group, m is the polymerization degree of monomer, and "- -" represents the cleavage bond site;
after desulphation, the final polymer product obtained inevitably carries polyethylene glycol groups.
In the invention, the polyethylene glycol group is positioned at the Z end of the RAFT chain transfer agent, and the reaction general formula for carrying out polymerization reaction is shown as follows:
wherein n is the polymerization degree of polyethylene glycol, R can represent any group, m is the polymerization degree of monomer, and "- -" represents the cleavage bond site;
it can be seen that after the desulphation, the final polymer product obtained is completely free of polyethylene glycol groups and does not affect the intrinsic composition of the final polymer product.
The embodiment of the invention also provides a preparation method of the RAFT chain transfer agent, and the reaction general formula is as follows:
the method comprises the following steps:
will beMixing metal hydride and carbon disulfide, and reacting to obtain polyethylene glycol thioester metal salt;
the polyethylene glycol thioester metal saltCarrying out substitution reaction to obtain the RAFT chain transfer agent;
wherein n is an integer of 1-1000, and X is selected from one of oxygen atom, sulfur atom and imino; a is a halogen atom; r is R 1 、R 2 Each independently selected from hydrogen atoms, substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 One of the alkyl groups, R 3 Selected from substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 Alkyl, substituted C 1 -C 18 Alkoxycarbonyl, unsubstituted C 1 -C 18 One of alkoxycarbonyl, substituted aryl, unsubstituted aryl, and cyano.
In the present embodiment, X is selected from one of an oxygen atom, a sulfur atom, and an imide group, that isSelected from-> One of them.
The preparation method provided by the embodiment of the invention is simple and efficient, and the RAFT chain transfer agent prepared by the method has good solubility in a wide pH water environment, does not introduce additional groups into the final product, and does not have additional influence on the properties of the final product.
In addition, compared with the traditional RAFT chain transfer agent obtained by condensing polyethylene glycol with a small molecular chain transfer agent with a specific functional group (the connecting bond between polyethylene glycol and a thioester chain transfer agent in the obtained chain transfer agent is easy to hydrolyze, and the R end of the small molecular chain transfer agent is required to be provided with a corresponding condensable functional group, so that the R group selection and the preparation method of the RAFT chain transfer agent are greatly limited), the RAFT chain transfer agent is prepared by a substitution reaction, the R group selection of the RAFT chain transfer agent is not limited, and the connecting bond between polyethylene glycol and the thioester chain transfer agent in the chain transfer agent is not hydrolyzed.
In this embodiment, a suitable solvent, such as tetrahydrofuran, may be selected according to practical needs.
In one embodiment, the metal hydride is selected from at least one of sodium hydride and potassium hydride, but is not limited thereto.
In one embodiment, the halogen atom is a chlorine atom, a bromine atom, or an iodine atom.
In one embodiment, theOne selected from benzyl bromide, (1-bromoethyl) benzene, bromobenzyl cyanide, and ethyl 2-bromo-2-methylpropionate, but not limited thereto.
The embodiment of the invention also provides a preparation method of the RAFT chain transfer agent, which has the following reaction general formula:
the method comprises the following steps:
will beMixing metal hydride, carbon disulfide and iodine, and reacting to obtain polyethylene glycol thioester disulfide;
the polyethylene glycol thioester disulfide is producedPerforming free radical exchange reaction on the (free radical) compound to obtain the RAFT chain transfer agent;
wherein n is an integer of 1-1000, and X is selected from one of oxygen atom, sulfur atom and imino; r is R 1 、R 2 Each independently selected from hydrogen atoms, substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 One of the alkyl groups, R 3 Selected from substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 Alkyl, substituted C 1 -C 18 Alkoxycarbonyl, unsubstituted C 1 -C 18 One of alkoxycarbonyl, substituted aryl, unsubstituted aryl, and cyano.
In the present embodiment, X is selected from one of an oxygen atom, a sulfur atom, and an imide group, that isSelected from-> One of them.
The preparation method provided by the embodiment of the invention is simple and efficient, and the RAFT chain transfer agent prepared by the method has good solubility in a wide pH water environment, does not introduce additional groups into the final product, and does not have additional influence on the properties of the final product.
In addition, compared with the traditional RAFT chain transfer agent obtained by condensing polyethylene glycol with a small molecular chain transfer agent with a specific functional group (the connecting bond between polyethylene glycol and a thioester chain transfer agent in the obtained chain transfer agent is easy to hydrolyze, and the R end of the small molecular chain transfer agent is required to be provided with a corresponding condensable functional group, so that the R group selection and the preparation method of the RAFT chain transfer agent are greatly limited).
In this embodiment, a suitable solvent, such as tetrahydrofuran, may be selected according to practical needs.
In one embodiment, the metal hydride is selected from at least one of sodium hydride and potassium hydride, but is not limited thereto.
In one embodiment, the polyethylene glycol thioester disulfide is free radical exchanged with a catalyst comprising, but not limited to, azobisisobutyronitrile or azobis (4-cyanopentanol) to yield the RAFT chain transfer agent.
The embodiment of the invention also provides application of the RAFT chain transfer agent in RAFT polymerization reaction. In this embodiment, the RAFT chain transfer agent is used to perform RAFT polymerization, so that the final polymer product obtained by the reaction does not contain polyethylene glycol groups at all, and the intrinsic composition of the final polymer product is not affected.
In a further embodiment, the RAFT polymerization is performed in an aqueous phase. One end of the RAFT chain transfer agent provided by the embodiment of the invention is connected with a polyethylene glycol group (water-soluble group), so that the RAFT chain transfer agent has good water solubility in a wide pH environment, and is particularly suitable for RAFT polymerization systems in an acidic and alkaline aqueous environment.
The following is a detailed description of specific examples.
EXAMPLE 1 Synthesis of benzylmethoxypolyethylene glycol trithiocarbonate
1.0g (0.5 mmol) of mercapto polyethylene glycol monomethyl ether, 12mg (0.5 mmol) of sodium hydride and 38mg (0.5 mmol) of carbon disulfide are added into a reactor, after the reaction is carried out for 1 hour, a tetrahydrofuran solution of benzyl bromide (containing 85.5mg (0.5 mmol) of benzyl bromide and 100mL of tetrahydrofuran) is added, after the reaction is carried out for 12 hours at room temperature, the solvent is filtered and removed, and the solution is dried in vacuum, thus obtaining the benzyl methoxy polyethylene glycol trithiocarbonate. Its nuclear magnetic hydrogen spectrum (CDCl) 3 ) As shown in FIG. 1, the successful preparation of benzylmethoxypolyethylene glycol trithiocarbonate can be demonstrated.
Example 2 2 Synthesis of Phenylethylmethoxy polyethylene glycol xanthate
1.0g (0.5 mmol) of polyethylene glycol monomethyl ether, 12mg (0.5 mmol) of sodium hydride and 38mg (0.5 mmol) of carbon disulfide are added into a reactor, after the reaction is carried out for 1 hour, a tetrahydrofuran solution of (1-bromoethyl) benzene (containing 92.5mg (0.5 mmol) of (1-bromoethyl) benzene and 100mL of tetrahydrofuran) is added, the mixture is reacted for 12 hours at room temperature, and then the solvent is filtered and removed, and the mixture is dried in vacuum, thus obtaining the 2-phenylethyl methoxy polyethylene glycol xanthate.
Example 3 1 Synthesis of nitrile benzyl methoxy polyethylene glycol carbamate
1.0g (0.5 mmol) of aminopolyethylene glycol monomethyl ether, 12mg (0.5 mmol) of sodium hydride and 38mg (0.5 mmol) of carbon disulfide are added into a reactor, after the reaction is carried out for 1h, a tetrahydrofuran solution containing bromobenzyl cyanide (containing 98.0mg (0.5 mmol) of bromobenzyl cyanide and 100mL of tetrahydrofuran) is added, after the reaction is carried out for 12h at room temperature, the solvent is filtered and removed, and the vacuum drying is carried out, thus obtaining the 1-nitrile benzyl methoxy polyethylene glycol carbamate.
EXAMPLE 4 Synthesis of ethoxycarbonyl isopropyl methoxy polyethylene glycol trithiocarbonate
1.0g (0.5 mmol) of mercapto polyethylene glycol monomethyl ether, 12mg (0.5 mmol) of sodium hydride and 38mg (0.5 mmol) of carbon disulfide are added into a reactor, after reaction for 1h, a tetrahydrofuran solution of ethyl 2-bromo-2-methylpropionate (containing 97.5mg (0.5 mmol) of ethyl 2-bromo-2-methylpropionate and 100mL of tetrahydrofuran) is added, after reaction for 12h at room temperature, the solvent is filtered and removed, and vacuum drying is performed to obtain ethoxycarbonyl isopropyl methoxy polyethylene glycol trithiocarbonate.
Example 5 2 Synthesis of Cyanoisopropyl methoxy polyethylene glycol trithiocarbonate
1.0g (0.5 mmol) of mercapto polyethylene glycol monomethyl ether, 12mg (0.5 mmol) of sodium hydride, 38mg (0.5 mmol) of carbon disulfide and 126.9mg (0.5 mmol) of iodine are added into a reactor, after reaction for 1h, a tetrahydrofuran solution of azobisisobutyronitrile (containing 41.0mg (0.25 mmol) of azobisisobutyronitrile and 100mL of tetrahydrofuran) is added, and after heating at 60 ℃ for reaction for 12h, the solvent is removed by filtration and dried in vacuo to obtain 2-cyano isopropyl methoxy polyethylene glycol trithiocarbonate. The nuclear magnetic hydrogen spectrum is shown in figure 2, and the obtained 2-cyano isopropyl methoxy polyethylene glycol trithiocarbonate is known.
Example 6 2 Synthesis of Cyanoisopropyl methoxy polyethylene glycol xanthate
1.0g (0.5 mmol) of polyethylene glycol monomethyl ether, 12mg (0.5 mmol) of sodium hydride, 38mg (0.5 mmol) of carbon disulfide and 126.9mg (0.5 mmol) of iodine are added into a reactor, after the reaction is carried out for 1h, a tetrahydrofuran solution of azobisisobutyronitrile (containing 41.0mg (0.25 mmol) of azobisisobutyronitrile and 100mL of tetrahydrofuran) is added, after the reaction is carried out for 12h by heating at 60 ℃, the solvent is removed by filtration after the reaction, and the solvent is dried in vacuum, thus obtaining the 2-cyano isopropyl methoxy polyethylene glycol xanthate.
EXAMPLE 7 Synthesis of (1-hydroxy-4-cyano-4-methyl) butyl methoxy polyethylene glycol carbamate
1.0g (0.5 mmol) of aminopolyethylene glycol monomethyl ether, 12mg (0.5 mmol) of sodium hydride, 38mg (0.5 mmol) of carbon disulfide and 126.9mg (0.5 mmol) of iodine are added into a reactor, after reaction for 1h, a tetrahydrofuran solution of azobis (4-cyanopentanol) (wherein, 63.0mg (0.25 mmol) of azobis (4-cyanopentanol) and 100mL of tetrahydrofuran are contained) is added, and after heating reaction for 12h at 60 ℃, the solvent is removed by filtration and dried in vacuo, thus obtaining the (1-hydroxy-4-cyano-4-methyl) butyl methoxy polyethylene glycol carbamate.
EXAMPLE 8 Synthesis of Poly (isopropyl acrylamide)
1.0g (8.8 mmol) of isopropyl acrylamide, 12mg (0.05 mmol) of ammonium persulfate, 38mg (0.03 mmol) of benzyl methoxy polyethylene glycol trithiocarbonate obtained in example 1 and water are added into a reactor to react for 48 hours at room temperature, 1.0g of 4,4' -azobis (cyanovaleric acid) is added, the reaction is heated at 60 ℃ for 24 hours, then the reaction is carried out in normal hexane, the solvent is removed and the reaction is carried out in vacuum, so that the poly isopropyl acrylamide is obtained, the nuclear magnetic hydrogen spectrum of the poly isopropyl acrylamide is shown as a graph in fig. 3, the occurrence of a signal peak without polyethylene glycol units can be clearly seen, and the RAFT chain transfer agent provided by the invention can effectively avoid polyethylene glycol modification and has no redundant modification on polymer products.
In summary, the invention provides the RAFT chain transfer agent, the preparation method and the application thereof, and one end of the RAFT chain transfer agent is connected with the polyethylene glycol group (water-soluble group), so that the RAFT chain transfer agent has good water solubility in a wide pH environment, and is particularly suitable for a RAFT polymerization system in an acid-base aqueous phase environment; in addition, because the polyethylene glycol group is positioned at the Z end of the RAFT chain transfer agent, the end of the polymer obtained by the RAFT polymerization reaction does not contain polyethylene glycol group modification, so that a polymer product completely free of polyethylene glycol chain segments can be obtained after the conventional desulfurization ester reaction, and the intrinsic composition of the polymer macromolecule obtained by the RAFT polymerization reaction is not influenced.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (9)
1. A RAFT chain transfer agent for aqueous phase polymerization, characterized in that a polyethylene glycol group is positioned at the Z-terminal of the RAFT chain transfer agent for aqueous phase polymerization; the RAFT chain transfer agent for aqueous phase polymerization has the structural general formula:
wherein n is an integer of 1 to 1000, X is one of oxygen atom, sulfur atom and imino group, R 1 、R 2 Each independently selected from hydrogen atoms, substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 One of the alkyl groups, R 3 Selected from substituted C 1 -C 18 Alkyl, unsubstituted C 1 -C 18 Alkyl, substituted C 1 -C 18 Alkoxycarbonyl, unsubstituted C 1 -C 18 One of alkoxycarbonyl, substituted aryl, unsubstituted aryl, and cyano.
2. The method of preparing RAFT chain transfer agent of claim 1, comprising the steps of:
will beMixing metal hydride and carbon disulfide, and reacting to obtain polyethylene glycol thioester metal salt;
the saidPolyethylene glycol thioester metal saltsCarrying out substitution reaction to obtain the RAFT chain transfer agent;
wherein A is a halogen atom.
3. The method according to claim 2, wherein the metal hydride is at least one selected from sodium hydride and potassium hydride.
4. The method according to claim 2, wherein the halogen atom is a chlorine atom, a bromine atom or an iodine atom.
5. The method of claim 4, wherein the steps ofSelected from one of benzyl bromide, (1-bromoethyl) benzene, bromobenzyl cyanide and ethyl 2-bromo-2-methylpropionate.
6. The method of preparing RAFT chain transfer agent of claim 1, comprising the steps of:
will beMixing metal hydride, carbon disulfide and iodine, and reacting to obtain polyethylene glycol thioester disulfide;
the polyethylene glycol thioester disulfide is producedAnd (3) carrying out free radical exchange reaction on the compound to obtain the RAFT chain transfer agent.
7. The method according to claim 6, wherein the metal hydride is at least one selected from sodium hydride and potassium hydride.
8. The method according to claim 6, wherein the RAFT chain transfer agent is obtained by subjecting the polyethylene glycol disulfide to a radical exchange reaction with azobisisobutyronitrile or azobis (4-cyanopentanol).
9. Use of the RAFT chain transfer agent of claim 1 in a RAFT polymerisation reaction, the RAFT polymerisation reaction being carried out in an aqueous phase.
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